Epoxylation products of unsaturated fatty acid amides and a process of preparing them



The present invention relates to epoxylation products and to a process of preparing them.

It has already been proposed to convert monoamides of unsaturated fatty acides into the corresponding epoxy derivatives using peracetic acid in glacial acetic acid. Thus, for example, it has already been described to prepare 9.10-epoxy-stearic acid amides, wherein at least one alkyl-, oxyalkyl-, aryl-, or acyl radical may be attached to the nitrogen atom.

Now we have found that highly epoxylated compounds containing for example more than about 75 percent of the theoretically possible content of epoxide oxygen can be obtained by reacting fatty acid diamides corresponding to the general formula R -NHR NH- R wherein at least one of the two substituents R and R res Patent represents a monoor polyunsaturated fatty acid radical containing at least 12 carbon atoms and having at least one isolated double bond which is separated from the CONH group by at least one saturated carbon atom, i.e. a carbon atom exclusively linked by saturated linkages, and wherein R represents a hydrocarbon radical containing at least 2 carbon atoms, the NH-groups being linked to different carbon atoms with peracids, especially peracetic acid or a mixture of formic acid and hydrogen peroxide in the presence of solvents or mixtures of solvents such as have a specific dissolving power. Solvents with a specific dissolving power are nonpolar solvents with a dielectric constant of more than 5, as far as they are stable with respect to the reactants and, especially, with regard to hydrogen peroxide and peracids, or mixtures consisting of at least one polar and at least one non-polar solvent which both are inert with respect to the reacants, in which mixture at least one solvent and the major proportion by weight possess a dielectric constant of more than 5. In the process carried through with the aid of peracetic acid, it is of advantage to operate in the presence of a mixture consisting of glacial acetic acid and a nonpolar solvent with a dielectric constant of more than 5, and in the process wherein a mixture of formic acid and hydrogen peroxide is used, it is advisable to operate in the presence of a single likewise nonpolar solvent, which only contains the small amounts of formic acid necessary to bring about epoxylation.

As substituents R and R there come into consideration, for example, the radical of oleic acid and/ or linoleic acid. Besides, it is possible to use diamides of mixtures of fatty acids which are rich in unsaturated compounds and which can be obtained on an industrial scale, for example from fats, such as the diamides of soyoil fatty acid. The radicals R and R can be both identical or different.

In the process of this invention it has proved to be particularly advantageous, especially as regards the working up of the reaction mixture, to use as solvent benzene which is halogenated, especially chlorinated or brominated in the nucleus, or the homologues thereof as far as these compounds are liquid, for example, chlorobenzene, orthoor meta-dichlorobenzene, chlorotoluene and/ or bromobenzene. In the process where peracetic acid is used, it is advisable to employ an inert polar solvent, especially glacial acetic acid, in admixture with a non-polar solvent, such as carbon tetrachloride, benzene, toluene, xylene, the aforesaid compounds which are halogenated in the nucleus or with liquid chlorinated hydrocarbons containing 2 carbon atoms, such as trichloroethylene and/ or dichloroethane.

In the case where the epoxylation is conducted with the use of peracetic acid it is advisable, as is known, not to allow the temperature to rise too much in the course of the reaction. The same applies to the case where a mixture of formic acid and hydrogen peroxide is used to efiect the reaction, but this latter process requires more time. In both processes the temperature applied is generally between about 10 and 60 C., preferably between about 20 and 40 C.

The amides used in the epoxylation process according to this invention can be obtained, for example, by reacting unsaturated fatty acid methyl esters or halides with dior polyamines. In this case, the amino groups may be attached to aromatic, hydroaromatic, alkyl aromatic or aliphatic radicals. The substituent R may also represent the ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, cyclohexane, phenylene, toluylene or xylylene radical. It is,however, particularly advantageous to use compounds in which the substituent R represents the ethylene radical.

The products obtained by the process of this invention are new and can be used with advantage in industry for making varnishes and plastics; they are used either in the form of the chief constituent or as an addition to coating compositions or as an addition to shaped bodies. Compositions or varnishes prepared with the use of the substances obtained by the process of this invention are distinguished by an excellent elasticity and an extraordinary resistance to the action of chemical agents.

It has already been proposed to eliect epoxylation processes with the use of formic acid and hydrogen peroxide, if desired in the presence of a solvent such as a saturated aliphatic hydrocarbon or an aromatic hydrocarbon or an aromatic hydrocarbon halogenated in the nucleus; in that case, however, other starting materials had been used and other reaction products having different properties had been obtained. Furthermore, it was impossible to forsee that the solvents according to this invention would be suitable for use in epoxylation processes.

The following examplesserve to illustrate the invention, but they are not intended to limit it thereto, the parts being by weight unless otherwise stated.

Example 1 parts of ethylene-bis-soyoil' fatty acid amide are dissolved in the hot in 500 cc. ofzcarbon tetrachloride, the solution is cooled, while stirring, to a temperature of 2030 C., so as to form a fine suspension into which is run a solution of 35 grams of peracetic acid (excess of 16 percent) in 270 cc. of glacial acetic acid. The temperature is preferably kept at 25 to 30 C. After 3 hours, the carbon tetrachloride is substantially distilled oif under reduced pressure and at a bath temperature of at most 30 C.; the residue is cooled, filtered 01f with suction and after-washed with water. After having been dried at 40 C. in a vacuum drying oven the crude product obtained can be used directly for further reactions; it is, however, also possible to recrystallize it, for example, from a mixture of acetone and alcohol in the proportion of 2:1.

Example 2 50 parts of ethylene-bis-soyoil fatty acid amide are dissolved in the hot in 400 cc. of chlorohenzene, the solution is cooled to 3540 C. so as to form a fine suspension to which are added 8 grams of formic acid (0.5 mol); at a temperature of 35,40 C, thereare added dropwise, 31 grams of hydrogen peroxide of, 35 percent strength. The reaction mixture is kept at that temperature for'24 to 26 hours and then evaporated to dryness under reduced pressure. The temperature of the bath should be raised only when the solvent has practically been removed by distillation. The solid residue can be molten under reduced pressure and at a temperature of 120-130 C. in order to remove the last traces of the adhering solvent.

We claim:

1. In a process for epoxylating unsaturated fatty acid amides with an epoxylating agent selected from the group consisting of peracetic acid and a mixture of formic acid and hydrogen peroxide, the improvement which comprises reacting a diamide of the general formula wherein R and R are acid radicals of acids of the group consisting of oleic, linoleic and soy oil fatty acids, and R is a divalent hydrocarbon selected from the group consisting of ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, cyclohexylene, phenylene, toluylene and xylylene groups, with said epoxylating agent at a temperature between about and 60 C. and in the presence of a non-polar solvent of the group consisting of benzene, toluene, xylene, the compounds thereof which are halogenated in the nucleus, carbon tetrachloride and liquid chlorinated hydrocarbons containing two carbon atoms. i

2. In a process for epoxylating unsaturated fatty acid amides with an epoxylating agent selected from the group consisting of peracetic acid and a mixture of formic acid and hydrogen peroxide, the improvement which comprises reacting a diamide of the general formula wherein R and R are acyl groups of soy oil fatty acids and R is a divalent hydrocarbon selected from the group consisting of ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, cyclohexylene, phenylene, toluylene and xylylene groups, with said epoxylating agent at a temperature between about 10 and 60 C. and in the presence of a non-polar solvent of the group consisting of benzene, toluene, xylene, the compounds thereof which are halogenated in the nucleus, carbon tetrachloride and liquid chlorinated hydrocarbons containing two carbon atoms.

3. In a process for epoxylating unsaturated fatty acid amides with an epoxylating agent selected from the group consisting of peracetic acid and a mixture of formic acid and hydrogen peroxide, the improvement which com prises reacting a diamide of the general formula R NH R NH--R wherein R and R are acyl groupsof soy oil fatty acids,

with said .epoxylating agent at a temperature between 4 about 10 and C. and in the presence of a non-polar solvent of the group consisting of benzene, toluene, xylene, the compounds thereof which are halogenated in the nucleus, carbon tetrachloride and liquid chlorinated hydrocarbons containing two carbon atoms.

4. In a process for epoxylating unsaturated fatty acid amides with peracetic acid, the improvement which comprises reacting a diamide of the general formula R CONHCH CH NHCOR wherein R CO- and R CO are acyl groups of soy oil fatty acids, with said peracetic acid at a temperature between about 10 and 60 C. and in the presence of carbon tetrachloride and glacial acetic acid.

.5. In a process for epoxylating unsaturated fatty acid amides with a mixture of formic acid and hydrogen peroxide, the improvement which comprises reacting a diamide of the general formula V R CONHCH CH NHCOR wherein R CO-- and R CO are acyl groups of soy oil fatty acids, with said formic acid and hydrogen peroxide at a temperature between about 10 and 60 C. and in the presence of chlorobenzene.

6. A polyepoxy diamidetof the general formula wherein R and R are acyl groups of epoxylated acids of the group consisting of oleic, linoleic and soy oil fatty acids, and R is a divalent hydrocarbon selected from the group consisting of ethylene, propylene, butylene, pentamethylene, hexamethylene, octamethylene, cyclohexylene, phenylene, toluylene and xylylene groups.

7. A polyepoxy diamide of the general formula wherein R and R are acyl groups of epoxylated acids of the group consisting of oleic, linoleic and soy oil fatty acids.

9. A polyepoxy diamide of the general formula R1CONHCH2CH2NHCOR3 wherein R CO- and R CO- are acyl groups of epoxylated soy oil fatty acids.

References Cited in the file of this patent UNITED STATES PATENTS 2,485,160 Niederhauser Oct. 18, 1949 2,543,419 Niederhauser Feb. 27, 1951 Scanlan Sept. 11, 1951 

1. IN A PROCESS FOR EPOXYLATING UNSATURED FATTY ACID AMIDES WITH AN EPOXYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF PERACETIC ACID AND A MIXTURE OF FORMIC ACID AND HYDROGEN PEROXIDE, THE IMPROVEMENT WHICH COMPRISES REACTING A DIAMIDE OF THE GENERAL FORMULA
 6. A POLYEPOXY DIAMIDE OF THE GENERAL FORMULA 